CN108239778A - A kind of preparation method of titanium alloy substrate surface high emissivity ceramic coating - Google Patents
A kind of preparation method of titanium alloy substrate surface high emissivity ceramic coating Download PDFInfo
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- CN108239778A CN108239778A CN201810045830.4A CN201810045830A CN108239778A CN 108239778 A CN108239778 A CN 108239778A CN 201810045830 A CN201810045830 A CN 201810045830A CN 108239778 A CN108239778 A CN 108239778A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- C—CHEMISTRY; METALLURGY
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
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Abstract
The invention discloses a kind of preparation method of titanium alloy substrate surface high emissivity ceramic coating, this method is：First, pre-grinding, pickling and flushing are carried out successively to titanium alloy surface；2nd, add water that electrolyte is made by calgon, sodium metasilicate and potassium fluorozirconate；3rd, titanium alloy is placed in stainless steel electrolytic slot, adds electrolyte, the titanium alloy carries out differential arc oxidation in titanium alloy surface using pulse mao power source equipment and prepare high emissivity ceramic coating as anode, the stainless steel electrolytic slot as cathode.The present invention is introduced into the component in electrolyte solution using differential arc oxidization technique in titanium alloy surface coating, and pass through substep Isobarically Control and adjust the ratio of each component in electrolyte solution, the improvement to the uniformity and compactness of titanium alloy substrate surface ceramic coat is realized in success, has prepared the titanium alloy surface ceramic coating that good combination power is had both with high emissivity.
Description
Technical field
The invention belongs to coating technology fields, and in particular to a kind of system of titanium alloy substrate surface high emissivity ceramic coating
Preparation Method.
Background technology
Titanium and its alloy have that density is small, intensity is high, good corrosion resistance and tensile property, and are led in aerospace
Domain is widely used as the structural material of aircraft and fuselage material.But the gas during high-speed flight is due to acutely being pressed
Strong friction can be generated with fuselage surface by contracting, and the kinetic energy of high-speed flow is converted into thermal energy and surface is added in boundary layer
Heat, the major part that the aircraft skin temperature of high-speed flight rises just derive from the energy, in addition prolonged sunlight irradiation
Also the temperature of fuselage can be caused constantly to increase.Can make after body temperature is excessively high the normal work of interior of aircraft electronic component by
It seriously affects, while the titanium alloy of fuselage outer layer also can generate oxidation at high temperature and oxygen is crisp, and thermal stability is caused drastically to decline,
Great negative effect is produced to the working performance of aircraft.It is therefore necessary to the titanium alloy material progress to aircraft surface
Certain surface treatment, the heat of accumulation is dissipated to play can in time by way of radiant heat transfer reduces aircraft table
The effect of face temperature.
Differential arc oxidization technique is a kind of emerging process for treating surface developed in recent years, is established in common anode oxygen
On the basis of change, workpiece is placed in electrolyte and applying voltage makes it generate micro-arc discharge, surface metal is mutual with electrolyte
Effect forms ceramic membrane.Differential arc oxidization technique and room temperature brushing, plasma spraying, surface deposition, anodic oxidation etc. are common
Matrix is strong with membranous layer binding force, and technical matters is simple to operation, and the thickness of film layer exists compared to having for titanium alloy surface treatment process
The advantages that controllable in a certain range, solves and is difficult in complex-shaped workpieces surface spraying or the non-uniform shortcoming of coating structure.
The transition metal oxide of multivalent state such as Fe2O3、NiO、CuO、Co2O3、MnO2、Cr2O3、TiO2、Ln2O3Deng due to
Its atom outermost layer has unpaired electron, is more easy to occur the transition of electron orbit, can be generated when it is mixed in appropriate crystal
Electric dipole moment so that the electron transition being difficult to happen under electric field action so as to improve spectral emissivity, therefore can be electrolysed
Multivalent state metal ion is introduced into matter solution to realize the generation of metal oxide in coating, so as to improve the emissivity of coating,
But the research for preparing the ceramic coating with high emissivity using differential arc oxidation at present is also fewer.
Invention content
The technical problems to be solved by the invention are in view of the above shortcomings of the prior art, to provide a kind of titanium alloy-based
The preparation method of body surface face high emissivity ceramic coating.The preparation method is using differential arc oxidization technique in titanium alloy surface coating
The component being introduced into electrolyte solution, and pass through substep Isobarically Control and adjust the ratio of each component in electrolyte solution, into
Work(realizes the improvement to the uniformity and compactness of titanium alloy substrate surface ceramic coat, has prepared with high emissivity,
The titanium alloy surface ceramic coating of good combination power is had both simultaneously.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of titanium alloy substrate surface high emissivity
The preparation method of ceramic coating, which is characterized in that this method includes the following steps：
Step 1: removing the burr around titanium alloy using grinding wheel, then pre-grinding processing is carried out to titanium alloy using sand paper,
The titanium alloy of removal surface oxide layer is obtained, is then immersed in pickling 5s~10s in mixed acid, then clean obtain is washed away with distilled water
The titanium alloy smooth to surface；
Step 2: water is added to be made electrolyte by calgon, sodium metasilicate and potassium fluorozirconate, six inclined phosphorus in the electrolyte
The content of sour sodium is 10g/L~30g/L, and the content of sodium metasilicate is 10g/L~20g/L, the content of potassium fluorozirconate for 0.5g/L~
3g/L；
Step 3: by step 1, treated that titanium alloy is placed in the stainless steel electrolytic slot equipped with electrolyte described in step 2
In, the titanium alloy is connected as anode with the anode of power supply, and the stainless steel electrolytic slot is as cathode and power cathode phase
Connection, the temperature for controlling electrolyte are 15 DEG C~30 DEG C, and substep Isobarically Control is carried out using pulse mao power source equipment：First
Differential arc oxidation 30min~40min under conditions of constant voltage is 500V~600V, then in the condition that constant voltage is 480V~580V
Lower differential arc oxidation 10min~20min, the time that boosting is controlled in micro-arc oxidation process are 60s~120s, frequency for 500Hz~
700Hz, duty ratio are 20%~30%, the finally surface using the clean titanium alloy of distilled water flushing and drying, then in titanium alloy
Surface obtains high emissivity ceramic coating；The high emissivity ceramic coating under conditions of being 5 μm~20 μm in infrared wavelength
Emissivity is 0.87~0.95.
A kind of preparation method of above-mentioned titanium alloy substrate surface high emissivity ceramic coating, which is characterized in that step 1
In titanium alloy surface is pre-processed using 240 mesh, 800 mesh, 1500 mesh sand paper successively.
A kind of preparation method of above-mentioned titanium alloy substrate surface high emissivity ceramic coating, which is characterized in that step 1
Described in mixed acid by HF solution and HNO3Solution mixes, and the mass percentage of HF is 7%, HNO in the mixed acid3
Mass percentage be 21%.
A kind of preparation method of above-mentioned titanium alloy substrate surface high emissivity ceramic coating, which is characterized in that step 3
The titanium alloy is placed in the middle part of stainless steel electrolytic slot, and the anode and cathode for ensureing differential arc oxidation ensure certain distance so that
Uniform high emissivity ceramic coating can be obtained during differential arc oxidation in titanium alloy surface.
A kind of preparation method of above-mentioned titanium alloy substrate surface high emissivity ceramic coating, which is characterized in that step 3
Described in stainless steel electrolytic slot outer wall on be provided with circulation for controlling electrolyte temperature, the circulation
Including the circulation pipe being wrapped on stainless steel electrolytic slot outer wall, the cycle for controlling electrolyte temperature is connected in the circulation pipe
Water, can just make the preparation of the coating not influenced by ambient temperature using the circulation, ensure that differential arc oxidation always can
Enough control carries out under conditions of 15 DEG C~30 DEG C.
A kind of preparation method of above-mentioned titanium alloy substrate surface high emissivity ceramic coating, which is characterized in that step 3
The thickness of the high emissivity ceramic coating is 20 μm~60 μm, and roughness is 3 μm~5 μm, the high emissivity ceramic coating
Bond strength with titanium alloy is 8MPa~15MPa.
Compared with the prior art, the present invention has the following advantages：
1st, the present invention is prepared for the ceramic coating of high emissivity using differential arc oxidization technique in titanium alloy surface.In differential of the arc oxygen
Using substep Isobarically Control during changing, so as to obtain the good coating of compactness.The dense coating and titanium alloy substrate
Metallurgical binding is realized, binding force is good, and bond strength is up to 8MPa~15MPa, and the thermal shock for arriving room temperature for 400 DEG C in temperature
50 secondary coatings are recycled in experiment not to be damaged and come off, and there is preferable thermal stability.The thickness and emission ratio of coating
It can be adjusted by controlling the component of voltage and electrolyte, it is simple for process to be easily achieved.
2nd, the present invention is using distribution pressure control method, and second of differential arc oxidation is lower than the voltage value of first time differential arc oxidation, this side
Method is more advantageous to improving coating compactness, and coordinate and add water that electrolyte is made by calgon, sodium metasilicate and potassium fluorozirconate, can
So that high emissivity thickness of ceramic coating prepared by differential arc oxidation is uniform, moderate and fine and close, calgon and silicon in electrolyte
Sour sodium can make film layer obtain higher compactness while thickness increase collectively as the main component of electrolyte.
3rd, high emissivity ceramic coating even structure prepared by the present invention, coating layer thickness reach 20 μm~60 μm, coating
Emissivity is 0.87~0.95, and the roughness of coating is 3 μm~5 μm, and recycles examination for 400 DEG C to room temperature of thermal shock in temperature
It tests 50 high emissivity ceramic coatings of middle cycle not to be damaged and come off, there is preferable thermal stability.
Technical scheme of the present invention is described in further detail below by drawings and examples.
Description of the drawings
Fig. 1 is the XRD diffraction patterns of high emissivity ceramic coating that the embodiment of the present invention 2 is prepared in TA6 titanium alloy surfaces.
Fig. 2 is the surface SEM of the high emissivity ceramic coating scannings that the embodiment of the present invention 2 is prepared in TA6 titanium alloy surfaces
Figure.
Fig. 3 is the section SEM of the high emissivity ceramic coating scannings that the embodiment of the present invention 2 is prepared in TA6 titanium alloy surfaces
Figure.
Specific embodiment
Embodiment 1
The method of the present embodiment includes the following steps：
Step 1: the burr around TC3 titanium alloys is removed, then with 240 mesh, 800 mesh, 1500 mesh sand paper pair using grinding wheel
TC3 titanium alloys are polished, and TC3 titanium alloys are immersed pickling 5s~10s in mixed acid after surface is smooth, the mixed acid is by HF
And HNO3Water is added to be mixed, the mass percentage of HF is 7%, HNO in the mixed acid3Mass percentage for 21%,
Pickling can get rid of TC3 titanium alloy surfaces greasy dirt and oxidation film, then fall remaining acid solution using distilled water flushing, and it is smooth to obtain surface
TC3 titanium alloys；
Step 2: water is added to be made electrolyte by calgon, sodium metasilicate and potassium fluorozirconate, six inclined phosphorus in the electrolyte
The content of sour sodium is 10g/L, and the content of sodium metasilicate is 10g/L, and the content of potassium fluorozirconate is 0.5g/L, calgon and silicic acid
Sodium is main salt system, and potassium fluorozirconate is additive；
Step 3: the TC3 titanium alloys of step 1 processing gained are placed in stainless steel electrolytic slot center, and to the electrolytic cell
The electrolyte being configured in middle addition step 2, makes TC3 titanium alloy samples submerge electrolyte, and positive pole TC3 titanium alloys are connected,
Power cathode connects with stainless steel electrolytic slot, opens the circulation being arranged on the outside of stainless steel electrolytic slot, it is ensured that electrolyte
Reaction temperature control at 15 DEG C, using pulse it is microarc oxidation equipment provided carry out substep Isobarically Control, the differential of the arc oxygen under constant pressure 500V
Change reaction 30min and then differential arc oxidation reacts 10min under 480V, and the time boosted in control micro-arc oxidation process is
60s, frequency 500Hz, duty ratio 20% is closed microarc oxidation equipment provided after reaction, and TC3 is taken out after voltage drops to 0V
Titanium alloy falls the remaining electrolyte of TC3 titanium alloy surfaces with distilled water flushing, is obtained after drying in TC3 titanium alloy surfaces occurred frequently
Penetrate rate ceramic coating.
In the present embodiment, circulation, the circulation packet are provided on the outer wall of the stainless steel electrolytic slot
The circulation pipe being wrapped on stainless steel electrolytic slot outer wall is included, the circulation pipe is interior by being used to control electrolyte temperature as 15 DEG C
Recirculated water.
The present embodiment is 20 μm in the thickness of high emissivity ceramic coating prepared by TC3 titanium alloy surfaces, and roughness is 5 μ
The bond strength of m, the high emissivity ceramic coating and TC3 titanium alloys is 8MPa；In the range of 5 μm~20 μm of infrared band
The emissivity of the high emissivity ceramic coating of preparation is 0.87, and is followed in temperature is 400 DEG C of thermal shock cyclic test to room temperature
50 high emissivity ceramic coatings of ring are not damaged and come off, and have preferable thermal stability.
Embodiment 2
The method of the present embodiment includes the following steps：
Step 1: the burr around TA6 titanium alloys is removed, then with 240 mesh, 800 mesh, 1500 mesh sand paper pair using grinding wheel
TA6 titanium alloys are polished, and TA6 titanium alloys are immersed pickling 5s~10s in mixed acid after surface is smooth, the mixed acid is by HF
And HNO3Water is added to be mixed, the mass percentage of HF is 7%, HNO in the mixed acid3Mass percentage for 21%,
Pickling can get rid of TA6 titanium alloy surfaces greasy dirt and oxidation film, then fall remaining acid solution using distilled water flushing, and it is smooth to obtain surface
TA6 titanium alloys；
Step 2: water is added to be made electrolyte by calgon, sodium metasilicate and potassium fluorozirconate, six inclined phosphorus in the electrolyte
The content of sour sodium is 15g/L, and the content of sodium metasilicate is 15g/L, and the content of potassium fluorozirconate is 2g/L, calgon and sodium metasilicate
For main salt system, potassium fluorozirconate is additive；
Step 3: the TA6 titanium alloys of step 1 processing gained are placed in stainless steel electrolytic slot center, and to the electrolytic cell
The electrolyte being configured in middle addition step 2, makes TA6 titanium alloy samples submerge electrolyte, and positive pole TA6 titanium alloys are connected,
Power cathode connects with stainless steel electrolytic slot, opens the circulation being arranged on the outside of stainless steel electrolytic slot, it is ensured that electrolyte
Reaction temperature control at 25 DEG C, using pulse it is microarc oxidation equipment provided carry out substep Isobarically Control, the differential of the arc oxygen under constant pressure 550V
Change reaction 35min and then differential arc oxidation reacts 15min under 530V, and the time boosted in control micro-arc oxidation process is
90s, frequency 600Hz, duty ratio 25% is closed microarc oxidation equipment provided after reaction, and TA6 is taken out after voltage drops to 0V
Titanium alloy falls the remaining electrolyte of TA6 titanium alloy surfaces with distilled water flushing, is obtained after drying in TA6 titanium alloy surfaces occurred frequently
Penetrate rate ceramic coating.
In the present embodiment, circulation, the circulation packet are provided on the outer wall of the stainless steel electrolytic slot
The circulation pipe being wrapped on stainless steel electrolytic slot outer wall is included, the circulation pipe is interior by being used to control electrolyte temperature as 25 DEG C
Recirculated water.
Fig. 1 is the XRD diffraction patterns of high emissivity ceramic coating that the present embodiment is prepared in TA6 titanium alloy surfaces, can from Fig. 1
It is mainly rutile, anatase and oxide TiO with the phase composition for finding out ceramic coating2, while matrix Ti is also detected.
Fig. 2 is the surface SEM scanning figures of high emissivity ceramic coating that are prepared in TA6 titanium alloy surfaces of the present embodiment, can be with from Fig. 2
Find out that coating surface is dispersed with a large amount of fine and closely woven discharge aperture, deposit is distributed in flakes on coating surface.Fig. 3 is this reality
Apply the section SEM scanning figures for the high emissivity ceramic coating that example is prepared in TA6 titanium alloy surfaces, as can be seen from Figure 3 coating with
Matrix is tightly combined, and has higher consistency, and discharge aperture is through coating surface.
The present embodiment is 45 μm in the thickness of high emissivity ceramic coating prepared by TA6 titanium alloy surfaces, roughness 3.6
μm, the bond strength of the high emissivity ceramic coating and TA6 titanium alloys is 15MPa；In 5 μm~20 μm of range of infrared band
The emissivity of the high emissivity ceramic coating of interior preparation is 0.95, and is recycled in temperature is 400 DEG C of thermal shock test to room temperature
50 times high emissivity ceramic coating is not damaged and comes off, and has preferable thermal stability.
Embodiment 3
The method of the present embodiment includes the following steps：
Step 1: the burr around TA7 titanium alloys is removed, then with 240 mesh, 800 mesh, 1500 mesh sand paper pair using grinding wheel
TA7 titanium alloys are polished, and TA7 titanium alloys are immersed pickling 5s~10s in mixed acid after surface is smooth, the mixed acid is by HF
And HNO3Water is added to be mixed, the mass percentage of HF is 7%, HNO in the mixed acid3Mass percentage for 21%,
Pickling can get rid of TA7 titanium alloy surfaces greasy dirt and oxidation film, then fall remaining acid solution using distilled water flushing, and it is smooth to obtain surface
TA7 titanium alloys；
Step 2: water is added to be made electrolyte by calgon, sodium metasilicate and potassium fluorozirconate, six inclined phosphorus in the electrolyte
The content of sour sodium is 30g/L, and the content of sodium metasilicate is 20g/L, and the content of potassium fluorozirconate is 3g/L, calgon and sodium metasilicate
For main salt system, potassium fluorozirconate is additive；
Step 3: the TA7 titanium alloys of step 1 processing gained are placed in stainless steel electrolytic slot center, and to the electrolytic cell
The electrolyte being configured in middle addition step 2, makes TA7 titanium alloy samples submerge electrolyte, and positive pole TA7 titanium alloys are connected,
Power cathode connects with stainless steel electrolytic slot, opens the circulation being arranged on the outside of stainless steel electrolytic slot, it is ensured that electrolyte
Reaction temperature control at 30 DEG C, using pulse it is microarc oxidation equipment provided carry out substep Isobarically Control, the differential of the arc oxygen under constant pressure 600V
Change reaction 40min and then differential arc oxidation reacts 20min under 580V, and the time boosted in control micro-arc oxidation process is
120s, frequency 700Hz, duty ratio 30% is closed microarc oxidation equipment provided after reaction, is taken out after voltage drops to 0V
TA7 titanium alloys fall the remaining electrolyte of TA7 titanium alloy surfaces with distilled water flushing, height are obtained in TA7 titanium alloy surfaces after drying
Emissivity ceramic coating.
In the present embodiment, circulation, the circulation packet are provided on the outer wall of the stainless steel electrolytic slot
The circulation pipe being wrapped on stainless steel electrolytic slot outer wall is included, the circulation pipe is interior by being used to control electrolyte temperature as 30 DEG C
Recirculated water.
The present embodiment is 60 μm in the thickness of high emissivity ceramic coating prepared by TA7 titanium alloy surfaces, and roughness is 3 μ
The bond strength of m, the high emissivity ceramic coating and TA7 titanium alloys is 12MPa；In 5 μm~20 μm of range of infrared band
The emissivity of the high emissivity ceramic coating of interior preparation is 0.91, and is recycled in temperature is 400 DEG C of thermal shock test to room temperature
50 times high emissivity ceramic coating is not damaged and comes off, and has preferable thermal stability.
The above is only presently preferred embodiments of the present invention, not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence change that art substantially makees above example, still fall within technical solution of the present invention
Protection domain in.
Claims (6)
1. a kind of preparation method of titanium alloy substrate surface high emissivity ceramic coating, which is characterized in that this method includes following
Step：
Step 1: removing the burr around titanium alloy using grinding wheel, then pre-grinding processing is carried out to titanium alloy using sand paper, obtained
The titanium alloy of surface oxide layer is removed, is then immersed in pickling 5s~10s in mixed acid, then washed away with distilled water and totally obtain table
The smooth titanium alloy in face；
Step 2: water is added to be made electrolyte by calgon, sodium metasilicate and potassium fluorozirconate, calgon in the electrolyte
Content for 10g/L~30g/L, the content of sodium metasilicate is 10g/L~20g/L, and the content of potassium fluorozirconate is 0.5g/L~3g/L；
Step 3: by step 1, treated that titanium alloy is placed in the stainless steel electrolytic slot equipped with electrolyte described in step 2,
The titanium alloy is connected as anode with the anode of power supply, and the stainless steel electrolytic slot is connected as cathode with power cathode
It connects, the temperature for controlling electrolyte is 15 DEG C~30 DEG C, and substep Isobarically Control is carried out using pulse mao power source equipment：First exist
Constant voltage is differential arc oxidation 30min~40min under conditions of 500V~600V, then under conditions of constant voltage is 480V~580V
Differential arc oxidation 10min~20min, the time that boosting is controlled in micro-arc oxidation process are 60s~120s, frequency for 500Hz~
700Hz, duty ratio are 20%~30%, the finally surface using the clean titanium alloy of distilled water flushing and drying, then in titanium alloy
Surface obtains high emissivity ceramic coating；The high emissivity ceramic coating under conditions of being 5 μm~20 μm in infrared wavelength
Emissivity is 0.87~0.95.
2. a kind of preparation method of titanium alloy substrate surface high emissivity ceramic coating according to claim 1, feature
It is, titanium alloy surface is pre-processed using 240 mesh, 800 mesh, 1500 mesh sand paper successively in step 1.
3. a kind of preparation method of titanium alloy substrate surface high emissivity ceramic coating according to claim 1, feature
It is, mixed acid described in step 1 is by HF solution and HNO3Solution mixes, and the quality percentage of HF contains in the mixed acid
It measures as 7%, HNO3Mass percentage be 21%.
4. a kind of preparation method of titanium alloy substrate surface high emissivity ceramic coating according to claim 1, feature
It is, titanium alloy described in step 3 is placed in the middle part of stainless steel electrolytic slot.
5. a kind of preparation method of titanium alloy substrate surface high emissivity ceramic coating according to claim 1, feature
It is, the circulation for controlling electrolyte temperature, institute is provided on the outer wall of stainless steel electrolytic slot described in step 3
It states circulation and includes the circulation pipe being wrapped on stainless steel electrolytic slot outer wall, be connected with to control electrolysis in the circulation pipe
The recirculated water of liquid temperature.
6. a kind of preparation method of titanium alloy substrate surface high emissivity ceramic coating according to claim 1, feature
It is, the thickness of high emissivity ceramic coating described in step 3 is 20 μm~60 μm, and roughness is 3 μm~5 μm, the high emission
The bond strength of rate ceramic coating and titanium alloy is 8MPa~15MPa.
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| CN112301400A (en) * | 2020-11-04 | 2021-02-02 | 西安赛福斯材料防护有限责任公司 | Preparation method of hard protection micro-arc oxidation film layer on surface of titanium alloy ball valve |
| CN112323114A (en) * | 2020-11-04 | 2021-02-05 | 西安赛福斯材料防护有限责任公司 | Preparation method of wear-resistant insulating film layer on surface of titanium alloy ball valve |
| CN112323114B (en) * | 2020-11-04 | 2022-08-23 | 西安赛福斯材料防护有限责任公司 | Preparation method of wear-resistant insulating film layer on surface of titanium alloy ball valve |
| CN112301400B (en) * | 2020-11-04 | 2023-06-20 | 西安赛福斯材料防护有限责任公司 | Preparation method of hard protection micro-arc oxidation film layer on surface of titanium alloy ball valve |
| CN113549957A (en) * | 2021-07-12 | 2021-10-26 | 西安理工大学 | Preparation method of anode mud-polyethylene composite anode plate |
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| CN108239778B (en) | 2019-08-13 |
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Denomination of invention: Preparation of High Emissivity Ceramic Coating on titanium alloy substrate Effective date of registration: 20200825 Granted publication date: 20190813 Pledgee: Weiyang sub branch of Shaanxi qinnong Rural Commercial Bank Co., Ltd Pledgor: XI'AN SURFACE MATERIAL PROTECTION Co.,Ltd. Registration number: Y2020610000130 |
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